Variable-temperature high-resolution solid-state C-13 NMR experiments were performed on poly-(di-n-alkylitaconate)s in bulk. Temperature-dependent line broadenings resulting from either motional modulation of the C-13-H-1 dipolar coupling or motional modulation of the chemical shift anisotropy were observed for each carbon atom of the polymer main chain and side chains. Similarly, independent determinations of the C-13-H-1 dipolar couplings and C-13 chemical shift anisotropies demonstrated the existence of local motions in solid poly-(di-n-alkylitaconate)s. All of these measurements led to a direct identification of the moving units that are involved in the various relaxations, which were previously investigated by using dielectric relaxation experiments.